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MOLECULAR STARK EFFECT MEASUREMENTS IN BROADBAND CHIRPED-PULSE FOURIER TRANSFORM MICROWAVE (CP-FTMW) SPECTROMETERS

Please use this identifier to cite or link to this item: http://hdl.handle.net/1811/33309

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dc.creator Alvarez-Valtierra, Leonardo en_US
dc.creator Shipman, Steven T. en_US
dc.creator Neill, Justin L. en_US
dc.creator Pate, Brooks H. en_US
dc.creator Lessari, Alberto en_US
dc.date.accessioned 2008-07-15T13:33:18Z
dc.date.available 2008-07-15T13:33:18Z
dc.date.issued 2008 en_US
dc.identifier 2008-WF-12 en_US
dc.identifier.uri http://hdl.handle.net/1811/33309
dc.description Emilsson, T. et al. en_US
dc.description Author Institution: Department of Chemistry, University of Virginia, McCormick Rd., P.O. Box 400319, Charlottesville, VA 22904; Universidad de Valladolid, Departmento Quimica Fisica y Quimica Inorganica, Facultad de Ciencias, Prado de la Magdalena, s/n, 47005 Valladolid, Spain en_US
dc.description.abstract We demonstrate the implementation of molecular Stark effect measurements in broadband, chirped-pulse Fourier transform microwave (CP-FTMW) spectrometers. For broadband spectroscopy, the dipole moment determination is performed by measuring the full, broadband spectrum (7 - 18 GHz) at a single electric field strength. The electric field strength is calibrated internally using the first order Stark shift of trifluoropropyne (2.317 D) which is added in a trace amount to the sample mixture. The molecular rotational spectrum in the applied electric field is fit to the rotational Hamiltonian with the rotational and distortion constants fixed at their field-free values. The only parameters varied in the fit are the Stark interaction terms (${\mu \cdot E}$) along each principal axis direction. The open interaction region available in CP-FTMW spectrometers makes it easy to incorporate simple electrode designs in the spectrometer. We use the ``Stark cage'' design previously described by Emilsson \textit{et al.}}, \textit{J. Chem. Phys.} \textbf{112} (2000), 1287-1294} We illustrate the effects of field inhomogeneity on broadband measurements. The performance of broadband molecular Stark effect measurements is benchmarked by comparing the new results to previous cavity-FTMW dipole moment determinations that track individual rotational transitions at several field strengths. The potential advantages of the broadband technique are suggested by the broadband Stark measurements of OCS where the dipole moments of several isotopomers and complexes are obtained from a single data set. en_US
dc.language.iso English en_US
dc.title MOLECULAR STARK EFFECT MEASUREMENTS IN BROADBAND CHIRPED-PULSE FOURIER TRANSFORM MICROWAVE (CP-FTMW) SPECTROMETERS en_US
dc.type Article en_US